If you want to increase harmonic distortion in the preamp, make your signal amplification stages more 'non-linear'. This tends to occur normally in tube preamps anyway, but you could consider things such as:
1) keeping more (rather than less) bypassing in the cathodes (This is because cathode current feedback makes everything 'more-linear' and so reduces harmonic distortion). Note if you want to include a cold clipper stage, which is usually unbypassed, keep this at the end of the preamp chain.
2) increase/steepen AC load line gradients (e.g., through higher AC loading after each gain stage - to get more asymmetry in each output signal swing - which means you'll probably need more stages to get more drive in the power amp)
3) don't use local NFB loops in your preamp (as these reduce harmonic distortion - i.e., same outcome as unbypassed cathodes)
4) Use 12AX7s (rather than 5751s, AT7s, AY7s, AU7s). Note that there are also reasons for breaking this rule - e.g. a 12AT7 in a Long Tail Pair inverter can sound really good and help a PP output stage to function 'better' in overdrive which IMO makes an amp sound nicer too.
5) Use dc-coupled pair normal gain stage and cathode follower like the 5F6A/marshall for the Tone stack driver (as these sound amazing when they're overdriven, but they also provide excellent buffering for a TMB tone stack when the amp is being played 'clean'). Note that this might seem somewhat contradictory to the aim in 2) above, but it in reality these act like one joined-up assymetrical gain stage when overdriven and IMO you gotta have it if you want a great sounding guitar amp.
6) If your aim is to get more even-order harmonics, then you should aim to keep as many 2nd, 4th etc harmonics of the fundamental in the signal as possible - and the 'best' way to achieve this is to have alternate hot and cold biasing in each successive preamp gain stage. You will still get some odd-order harmonics if you do this, but you will get 'more of a mix' of even-order and odd-order harmonics. (Otherwise, if all preamp stages are centre-biased, then when these are driven into 'symmetrical clipping', the result is more odd-order harmonics, which probably will sound 'harsher' - which might or might not suit you). Note that will all the gain that you will get if you have 3 or more preamp stages in the preamp, you'll want some inter-stage attenuation otherwise you'll end up with mush.
YMMV.